Abrasion resistant microsphere articles

Abstract

There is provided an article having a compliant article where the compliant article comprises an polymer layer and a first layer disposed along a first major surface of the polymer layer; and a plurality of microspheres partially embedded and adhered to a major surface of the first layer opposite the surface that is disposed along the first major surface of the polymer layer, wherein the article has a compression modulus of less than or equal to 0.5 MPa. There is also provided an article having a compliant article where the compliant article comprises a polymer layer; and a plurality of microspheres partially embedded and adhered to a major surface of the compliant article, where the article has a compression modulus of less than or equal to 0.5 MPa, and further where the article is a decorative article.

1 . An article comprising:
 (a) a compliant article wherein the compliant article comprises an polymer layer and a first layer disposed along a first major surface of the polymer layer; and   (b) a plurality of microspheres partially embedded and adhered to a major surface of the first layer opposite the surface that is disposed along the first major surface of the polymer layer,   wherein the article has a compression modulus of less than or equal to 0.5 MPa.   
     
     
         2 . The article of  claim 1  wherein the first layer is selected such that the article exhibits a stain resistance to yellow mustard at elevated temperature and humidity as measured by the change in b* of less than 70. 
     
     
         3 . The article of  claim 1 , wherein the thickness of the compliant article is greater than 50 microns. 
     
     
         4 . The article of  claim 1 , wherein the first layer is selected from at least one of linear resins and resins having low cross link densities. 
     
     
         5 . The article of  claim 4 , wherein the linear resins are selected from at least one of the following linear materials: polyurethanes, polyureas, polyurethane ureas, polypolyesters, polycarbonate, ABS, polyolefins, acrylic and methacrylic acid ester polymers and copolymers, polyvinyl chloride polymers and copolymers, polyvinyl acetate polymers and copolymers, polyamide polymers and copolymers, fluorine containing polymers and copolymers, silicones, silicone containing copolymers, thermoplastic elastomers, such as neoprene, acrylonitrile butadiene copolymers, and combinations thereof. 
     
     
         6 . The article of  claim 4  wherein the article has an elongation percent at failure of greater than 26%. 
     
     
         7 . The article of  claim 1  wherein the plurality of microspheres are selected from at least one of glass, polymers, glass ceramics, ceramics, metals and combinations thereof. 
     
     
         8 . The article of  claim 1  further comprising a second layer disposed along the second major surface of the compliant article. 
     
     
         9 . The article of  claim 8  wherein the second layer comprises a flexible material. 
     
     
         10 . The article of  claim 1  wherein the article is resistant to organic solvents. 
     
     
         11 . The article of  claim 1  wherein the article exhibits a coefficient of friction of less than or equal to 0.3. 
     
     
         12 . The article of  claim 1  wherein the article is heat bonded at elevated temperatures to a substrate. 
     
     
         13 . The article of  claim 1  wherein the polymer layer comprises an aliphatic polyurethane polymer comprising a plurality of soft segments, and a plurality of hard segments, wherein the soft segments comprise poly(alkoxy) polyol, polycarbonate polyol or combinations thereof, and wherein the soft segment is essentially free of crosslinker. 
     
     
         14 . The article of  claim 13  wherein the soft segments have a number average molecular weight of less than 10,000 g/mol, and wherein the hard segments are derived from diols having molecular weights of less than 600 g/mol. 
     
     
         15 . The article of  claim 13  wherein the soft segments have a number average molecular weight of at least 500 g/mol. 
     
     
         16 . The article of  claim 13  wherein the soft segments have a number average molecular weight of 500 g/mol to 6,000 g/mol. 
     
     
         17 . The article of  claim 13  wherein the soft segments have a number average molecular weight of 500 g/mol to 3,000 g/mol. 
     
     
         18 . The article of  claim 13  wherein the compliant article has a thickness of 50 to 600 microns, and includes microspheres having an average diameter of about 30 to 200 microns. 
     
     
         19 . The article of  claim 13  wherein the aliphatic polyurethane polymer contains less than 50 percent by weight hard segments and 15 to 90 percent by weight soft segments. 
     
     
         20 . The article of  claim 13  wherein the total amount of hard and soft segments in the aliphatic polyurethane polymer is at least 90 percent by weight of the polymer. 
     
     
         21 . The article of  claim 1  further comprising at least one additional layer disposed between the first layer and the polymer layer. 
     
     
         22 . The article of  claim 21  further comprising a second additional layer disposed between the polyurethane layer and the polymer layer. 
     
     
         23 . An article comprising:
 (a) a compliant article wherein the compliant article comprises a polymer layer; and   (b) a plurality of microspheres partially embedded and adhered to a major surface of the compliant article,   wherein the article has a compression modulus of less than or equal to 0.5 MPa, and further wherein the article is a decorative article.   
     
     
         24 . The article of  claim 23  wherein the compliant article further comprises a first layer disposed between the polymer layer and the plurality of microspheres. 
     
     
         25 . The article of  claim 24  wherein the first layer is selected such that the article exhibits a stain resistance to yellow mustard at elevated temperature and humidity as measured by the change in b* of less than 70. 
     
     
         26 . The article of  claim 23 , wherein the thickness of the compliant article is greater than 50 microns. 
     
     
         27 . The article of  claim 24  wherein the first layer is selected from at least one of linear resins and resins having low cross link densities. 
     
     
         28 . The article of  claim 27 , wherein the linear resins are selected from at least one of the following linear materials: polyurethanes, polyureas, polyurethane ureas, polypolyesters, polycarbonate, ABS, polyolefins, acrylic and methacrylic acid ester polymers and copolymers, polyvinyl chloride polymers and copolymers, polyvinyl acetate polymers and copolymers, polyamide polymers and copolymers, fluorine containing polymers and copolymers, silicones, silicone containing copolymers, thermoplastic elastomers, such as neoprene, acrylonitrile butadiene copolymers, and combinations thereof. 
     
     
         29 . The article of  claim 27  wherein the article has an elongation percent at failure of greater than 26%. 
     
     
         30 . The article of  claim 23  wherein the plurality of microspheres are selected from at least one of glass, polymers, glass ceramics, ceramics, metals and combinations thereof. 
     
     
         31 . The article of  claim 23  further comprising a second layer disposed along the second major surface of the compliant article. 
     
     
         32 . The article of  claim 23  wherein the second layer comprises a flexible material. 
     
     
         33 . The article of  claim 23  wherein the article is resistant to organic solvents. 
     
     
         34 . The article of  claim 23  wherein the article exhibits a coefficient of friction of less than or equal to 0.3. 
     
     
         35 . The article of  claim 23  wherein the article is heat bonded at elevated temperatures to a substrate. 
     
     
         36 . The article of  claim 23  wherein the polymer layer comprises an aliphatic polyurethane polymer comprising a plurality of soft segments, and a plurality of hard segments, wherein the soft segments comprise poly(alkoxy) polyol, polycarbonate polyols, or combinations thereof, and wherein the soft segment is essentially free of crosslinker. 
     
     
         37 . The article of  claim 36  wherein the soft segments have a number average molecular weight of less than 10,000 g/mol, and wherein the hard segments are derived from diols having molecular weights of less than 600 g/mol. 
     
     
         38 . The article of  claim 36  wherein the soft segments have a number average molecular weight of at least 500 g/mol. 
     
     
         39 . The article of  claim 36  wherein the soft segments have a number average molecular weight of 500 g/mol to 6,000 g/mol. 
     
     
         40 . The article of  claim 36  wherein the soft segments have a number average molecular weight of 500 g/mol to 3,000 g/mol. 
     
     
         41 . The article of  claim 36  wherein the polymer layer has a thickness of 50 to 600 microns, and includes microspheres having an average diameter of about 30 to 200 microns. 
     
     
         42 . The article of  claim 36  wherein the polyurethane polymer contains less than 50 percent by weight hard segments and 15 to 90 percent by weight soft segments. 
     
     
         43 . The article of  claim 36  wherein the total amount of hard and soft segments in the polyurethane polymer is at least 90 percent by weight of the polymer. 
     
     
         44 . The article of  claim 1  wherein the article has a gloss change at 85° Angle of less than or equal to 1.00 according the Abrasion Resistance Test. 
     
     
         45 . The article of  claim 23  wherein the article has a gloss change at 85° Angle of less than or equal to 1.00 according the Abrasion Resistance Test.